邓亚运,庄英滢,冯 越,陆思源,程家高,徐晓勇,2*(.华东理工大学药学院药物化工所,上海市化学生物学重点实验室,上海 200237；2.上海生物制造技术协同创新中心,上海 200237)



顺硝烯新烟碱杀虫剂环氧虫啶在水中的光降解

邓亚运1,庄英滢1,冯 越1,陆思源1,程家高1,徐晓勇1,2*(1.华东理工大学药学院药物化工所,上海市化学生物学重点实验室,上海 200237；2.上海生物制造技术协同创新中心,上海 200237)

摘要：为了正确评估新型杀虫剂环氧虫啶(CYC)的环境风险,了解环氧虫啶在水环境中的光降解规律,探讨了CYC初始浓度、温度、初始pH值、过氧化氢浓度及硝酸根对CYC光降解的影响.结果表明,CYC的光降解符合一级动力学反应.直接光降解中,随浓度降低、温度升高,光解速率加快,环氧虫啶的反应活化能为21.27kJ/mol.通过测定CYC的pKa值为3.42以及模拟计算CYC不同粒子形式的光反应活性,可知pH值对CYC光解的影响较为复杂:酸性条件下,CYC的降解速率取决于其形态(阳离子和中性粒子)与单线态能量;碱性条件下,降解速率主要受羟基自由基数量的影响.间接光降解中,硝酸根和过氧化氢对CYC光解均表现为促进作用.在评估环氧虫啶的环境风险时,应综合考虑环境因素对其降解的影响.

关键词：新烟碱类杀虫剂；环氧虫啶；光降解；羟基自由基；HOMO-LUMO值

* 责任作者, 教授, xyxu@ecust.edu.cn

近年来,新烟碱类杀虫剂被认为是农业领域的里程碑[1].是自拟除虫菊酯商业化后销售量增长最快的一类农药,其全球销量占整个杀虫剂市场的24%,约为26.32亿美元[2].至今为止,已经商业化的新烟碱类杀虫剂包括吡虫啉、噻虫啉等.当杀虫剂在田间喷洒至土壤表面、水体和植物表面之后,它们将在自然环境中经历生物降解、水解及光解过程,在这些变化过程中往往会对环境产生负面的影响,因而必须进行其环境行为的研究.有关新烟碱杀虫剂光降解研究已有报道[1,4-5], Peña等[6]研究了噻虫嗪和噻虫啉在污水、溶解有机质和表面活性剂的水溶液中的光降解.

作为对吡虫啉的抗性害虫具有显著活性的新烟碱杀虫剂,环氧虫啶(CYC)具有良好的市场前景,Shao等[7]在2010年首次对它进行了报导.该杀虫剂由华东理工大学李忠教授等设计合成,具有广谱和高效的杀虫活性,极有前景进入市场成为国际上具有重要影响力的新一类杀虫剂.因而很有必要进行环氧虫啶环境行为的研究,为环氧虫啶的进一步开发和安全合理使用以及最终消除可能产生的环境污染提供科学依据. Liu 等[8]研究了环氧虫啶在淹水无氧土壤中的降解情况.然而关于环氧虫啶在水环境中的光稳定性还缺乏研究.

本文对环氧虫啶在水中的光稳定性进行了研究,包括直接光降解和间接光降解两部分.考察了浓度、温度、pH值、过氧化氢及硝酸根等影响因素,以期为评价环氧虫啶的环境特性提供科学依据.

1　材料与方法

1.1 材料

用于HPLC分析的乙腈为色谱纯,购自Merck公司;MilliQ超纯水(Milli-pore, 18MΩ·cm);环氧虫啶标准品(实验室自制,含量≥99.0%).其它试剂均为分析纯.

1.2 仪器

XPA系列走马灯式旋转光反应仪(南京胥江机电厂);Agilent 1200液相色谱仪,二极管阵列(DAD)检测器;光电分析天平,Mettler Toledo EL204,精确到0.1mg;pH精密酸度计,雷磁PHS-3C;Sirius T3理化常数仪.

1.3 实验方法

使用Sirius T3理化常数仪进行空白样实验,测定试验参数,测定环氧虫啶的pKa值.

采用Chemoffice软件构建小分子三维结构,采用Gaussian软件,分别计算环氧虫啶小分子的HOMO和LUMO值并计算轨道差,预测环氧虫啶不同状态下的反应活性.

用超纯水准确配制环氧虫啶的溶液,同时添加不同浓度的化合物作为影响因子,取新鲜配制的溶液于50mL石英试管中,置于光化学反应仪上,进行光照反应,并设置铝箔包裹的黑暗对照.灯源为300W高压汞灯,光照时石英试管距光源10cm.间隔一定时间取样,对样品进行HPLC分析.在pH对环氧虫啶光降解影响实验中,用NaOH和HCl调节超纯水的pH值,并使用该pH的溶液配制环氧虫啶溶液.

采用一级反应动力学描述光解反应,并使用ln(Ct/C0)-t线性拟合得到一级反应速率常数k.公式T1/2=ln2/k计算半衰期.

1.4 分析方法

CYC的定量分析采用Agilent 1200液相色谱分析.分析柱为Zobarx Extend-C18 (5μm, 250mm×4.6mm),柱温25℃.流速为1ml/min,紫外检测波长为340nm,自动进样,进样量为10μL.流动相为甲醇/水=30:70(体积比),样品运行时间为6min.此分析条件下,环氧虫啶的保留时间为4.39min.

2　结果与讨论

2.1 环氧虫啶的直接光降解

2.1.1 浓度对环氧虫啶光降解的影响 从表1和图1可见,浓度为5×10-5,1×10-4, 2× 10-4mol/L的环氧虫啶光降解速率常数分别为0.0911,0.0578,0.0294min-1,环氧虫啶初始浓度增加,光降解速率常数k减小.与Orellana-García等[9]对除草剂氨基三唑、二氯吡啶酸、氯氟吡氧乙酸、二氯苯二甲脲光解的研究结果一致.本研究中同时也进行了对照暗反应实验,结果表明环氧虫啶在无光照下没有降解,说明水解或生物降解对环氧虫啶的光降解没有贡献.

2.1.2 温度对环氧虫啶光降解的影响 实验结果见表1与图2,表明温度对环氧虫啶光解有重要影响.15℃,25℃,35℃下,环氧虫啶光降解半衰期对应为11.04,7.61,6.21min.15℃时环氧虫啶的光降解速率仅为35℃的56.25%.可见升高环境温度,环氧虫啶光降解速率常数增加,反应加快.环氧虫啶的光降解速率常数与温度之间的关系,遵循Arrhenius-type经验式:

表1　环氧虫啶在不同条件下的光降解动力学常数Table 1　Cycloxaprid photodegradation kinetics constants under different conditions

图1　不同底物浓度对环氧虫啶直接光降解的影响Fig.1　Effect of initial concentration on direct photolysis of CYC in Milli-Q water

式中:k是反应速率常数,min-1;T是绝对温度,K.

环氧虫啶的反应活化能为21.27KJ/mol.温度影响环氧虫啶的光降解,因而在考察其他因素的影响时,实验温度严格控制为25℃.

图2　温度对环氧虫啶直接光降解的影响Fig.2　Effect of temperature on direct photolysis of CYC in Milli-Q water

2.1.3 pH值对环氧虫啶光降解的影响 很多研究表明,溶液的pH值能够显著影响有机化合物的光降解[10].Bagal等[15]研究表明pH值降低2,4-二硝基苯酚的光降解速率变慢,这是由于低pH值下,2,4-二硝基苯酚为中性粒子,比阴离子状态对光敏感.Zhou等[16]研究对氨基苯甲酸的光解,发现对氨基苯甲酸的光降解速率随着pH值的增大而加快.Benitez等[17]发现高pH值环境抑制苯并三唑和N,N-二乙基间甲苯甲酰胺的光降解.

初始浓度为5×10-5mol/L的环氧虫啶在不同pH条件下的光降解情况如图3和表1所示.pH 3.00,4.76,7.63,9.20,10.05条件下对应的环氧虫啶光降解速率常数分别为1.0622,0.0931,0.0911, 0.0501,0.0391min-1.可见,pH值对水中环氧虫啶的光降解具有非常重要的影响,随着pH值的增加,环氧虫啶的光降解变慢.通过Sirius T3理化常数测定仪测得环氧虫啶的pKa值为3.42,因此,水溶液中,环氧虫啶存在中性分子和阳离子两种状态.pH<7时,随pH值降低,环氧虫啶在溶液中阳离子含量增加;pH>7时,溶液中环氧虫啶以中性分子形式存在.基于以上结果,猜测环氧虫啶的阳离子光反应活性高于环氧虫啶中性分子.Zhou 等[16]利用DFT计算出对氨基苯甲酸的各粒子形态的单线态能量值,发现其光降解反应速率与该值有关.单线态能量值越小,粒子越易发生光反应,即光降解速率越快.为验证猜想,我们也利用Gaussian 03计算环氧虫啶不同粒子的LOMOHOMO值.如图4所示,环氧虫啶存在两种不同的构型,左图为它们的中性分子状态,右图为阳离子, 在(a)构型下的阳离子LOMO-HOMO值为3.89eV,中性分子为4.50eV;环氧虫啶在(b)构型下的阳离子为3.95eV,中性分子为4.64eV.比较两种构型中阳离子和中性分子的LOMO-HOMO值,可知环氧虫啶的阳离子均比中性分子所需活化能低.环氧虫啶的阳离子更易发生光降解反应,当溶液中环氧虫啶阳离子的含量增多时,光降解速率加快.以上结论合理地解释了环氧虫啶处于酸性环境中光降解比碱性环境中快的现象.

图3　pH值对环氧虫啶光降解的影响Fig.3　Effect of initial pH value on the photodegradation of cycloxaprid

碱性条件下,溶液中的环氧虫啶以中性分子形式存在,其含量不再随pH值变化而改变.而由表1可知,pH 7.63,9.20,10.05条件下对应的环氧虫啶光降解半衰期存在差异,分别为7.61,13.84, 17.73min.因此,碱性条件下,环氧虫啶的光降解速率随着pH增加而变慢的现象与环氧虫啶本身性质无关.可能是由于: a)高pH值环境下,碱性降解产物的累积抑制光降解过程; b)随着pH值的增加,羟基自由基的氧化性降低[18]; c)碱性条件下,羟基自由基迅速消亡[19].Xu等[19]研究邻苯二甲酸二甲酯的光降解,发现碱性溶液中羟基自由基的含量降低导致邻苯二甲酸二甲酯的光降解变慢,如式(2)、(3)所示.

图4　两种构型的环氧虫啶的阳离子和中性分子结构Fig.4　The cations and neutral particles of two configuration for cycloxaprid

猜测在碱性条件下,环氧虫啶的光降解速率与溶液中羟基自由基的含量有关.为验证猜测,进一步设计实验,在不同pH值的环氧虫啶溶液中加入1%叔丁醇作为羟基自由基捕获剂.结果表明pH为3.00时,加入叔丁醇并未对环氧虫啶的光降解产生明显影响.然而pH9.20时,叔丁醇的加入使得环氧虫啶的光解速率仅为原先的55.29%.叔丁醇显著减弱该条件下环氧虫啶的光降解.因此,在碱性条件下,羟基自由基是环氧虫啶光降解的主要因素.

结合图表的数据及结论,发现环氧虫啶光降解与两个因素有关:一是环氧虫啶本身的性质,二是溶液中羟基自由基的含量.当pH<7时,环氧虫啶本身的性质决定了光降解速率,羟基自由基对环氧虫啶光降解反应的贡献小;当pH>7时,溶液中羟基自由基的含量成为决定性因素.

2.2 环氧虫啶的间接光降解

2.2.1 过氧化氢对环氧虫啶光降解的影响 许多研究表明,高浓度的过氧化氢对于化合物的光降解具有促进作用[20].然而,也有研究表明,光降解速率并不随过氧化氢浓度的增加一直增加,对于不同的化合物,存在最适宜的过氧化氢浓度[25].为确定过氧化氢对环氧虫啶光降解的影响,实验研究了过氧化氢浓度为2×10-3mol/L, 5× 10-3mol/L,1×10-2mol/L和1.5×10-2mol/L时环氧虫啶的光降解情况.由图5和表1可以看出,过氧化氢的浓度从0mol/L增加到1×10-2mol/L时,环氧虫啶的光降解速率也随之增加;然而当过氧化氢的浓度增至1.5×10-2mol/L时,相比于1× 10-2mol/L,降解速率反而减小.

图5　过氧化氢对环氧虫啶光降解的影响Fig.5　Effect of initial H2O2 concentration on the photodegradation of cycloxaprid

2×10-3mol/L浓度的H2O2条件下,环氧虫啶光降解速率常数是超纯水中光降解速率的2.93 倍. 5×10-3mol/L,1×10-2mol/L和1.5×10-2mol/L浓度的过氧化氢条件下,环氧虫啶的光降解速率常数依次变为原来的5.13,7.71和4.89倍.数据显示,过氧化氢具有明显的加速作用.这主要是因为低浓度的过氧化氢在光照下会生成羟基自由基,加速光降解的进行,如下式[27]:

但过氧化氢加速光降解反应存在最优化浓度,过氧化氢浓度为1.5×10-2mol/L的降解速率常数比1×10-2mol/L时的降解速率常数降低36.56%.这主要是由于随着过氧化氢浓度的增加,溶液中未被光照激发成羟基自由基的过氧化氢会与生成的羟基自由基反应,反而降低了溶液中羟基自由基的含量,可由式(5)～(7)表述[28].

2.2.2 硝酸根对环氧虫啶光降解的影响 硝酸根离子普遍存在于自然水体中,其浓度因地理位置的差异而略有不同,水环境浓度一般为1× 10-5～1×10-3mol/L[29].硝酸根在光照下产生成·NO2和·OH等活性自由基,从而促进化合物的间接光降解[30],如(8)～(9)所示[33]:

图6和表1显示,硝酸根浓度为0,1×10-4,1× 10-3和2×10-3mol/L时,环氧虫啶光降解的半衰期分别为7.61,7.18,6.29,5.41min,半衰期随着硝酸根浓度的增加而缩短.这是由于光敏态的NO3-促进羟基自由基的产生,从而加快环氧虫啶的光降解.然而,相对于不加硝酸根,加入2×10-3mol/L硝酸根,环氧虫啶的光降解半衰期只缩短了28.9%.说明,相对于环氧虫啶在水环境中的直接光降解,硝酸根对环氧虫啶的间接光降解作用为次要的.光敏剂硝酸根的存在并不能显著影响水环境中环氧虫啶的光降解行为.

图6　硝酸根对环氧虫啶光降解的影响Fig.6　Effect of initial nitrate concentration on the photodegradation of cycloxaprid

3　结论

3.1 环氧虫啶的光降解反应可用一级动力学方程模拟.环氧虫啶初始浓度增加,光降解速率常数k减小;温度对环氧虫啶光降解有促进作用,温度升高,环氧虫啶光降解加快,环氧虫啶的反应活化能(Ea)为21.27kJ/mol.

3.2 溶液pH值影响环氧虫啶的光降解速率.通过测定环氧虫啶的pKa值为3.42,确定环氧虫啶在不同pH值溶液中的主要存在形式.当pH值小于7时,随着pH值的减小,环氧虫啶在水溶液中的阳离子含量增多.通过高斯计算,确定了环氧虫啶阳离子的光反应活性高于中性分子.在酸性环境下,环氧虫啶的光降解由环氧虫啶本身性质即在水中阳离子的含量决定;当pH值大于7时,环氧虫啶在水溶液中以中性分子形式存在,羟基自由基对环氧虫啶的光降解起决定性作用.

3.3 过氧化氢加快环氧虫啶的光降解速率,但是光降解速率并不随过氧化氢浓度增加而一直增加,存在最适宜浓度;硝酸根也能促进环氧虫啶的光降解,但促进作用相对较弱.

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Photodegradation of cis-configuration neonicotinoid cycloxaprid in water.

DENG Ya-yun1, ZHUANG Ying-ying1, FENG Yue1, LU Si-yuan1, CHENG Jia-gao1, XU Xiao-yong1,2*(1.Shanghai Key Lab of Chemistry Biology, Institute of Pesticides and Pharmaceuticals, East China University of Science and Technology, Shanghai 200237, China；2.Shanghai Collaborative Innovation Center for Biomanufacturing Technology, Shanghai 200237, China). China Environmental Science, 2016,36(4)：1112～1118

Abstract：In order to correctly evaluate the environmental risk of the new insecticide CYC, the influence of the CYC initial concentration, temperature, initial pH, concentration of hydrogen peroxide and nitrate on the CYC photodegradation in water were studied. The results show that the photodegradation of cycloxaprid was fitted to pseudo-first-order kinetics reaction. For direct photodegradation, cycloxaprid photolysis rate was accelerated with the decreasing of CYC concentration and the increase of temperature. The activation energy of photochemical reaction was 21.27kJ/mol. By measuring the CYC pKa value of 3.42 and simulation CYC reactivity of different forms of light particles, known the complicated influence of pH value on CYC photolysis: In the acidic conditions, the degradation rate of cycloxaprid depended on the different cycloxaprid forms (cations and neutral particles) and their singlet energy values. While, in the alkaline condition, the photodegradation rate was mainly affected by the number of hydroxyl radicals in the solution. For CYC indirect photodegradation, nitrate and hydrogen peroxide were confirmed to promote the role. When evaluating the environmental risk of CYC should comprehensively consider the effect of environmental factors on its degradation.

Key words：insecticide；cycloxaprid；photodegradation；hydroxyl radical；HOMO-LUMO gap

作者简介：邓亚运(1990-),女,湖北咸宁人,华东理工大学药学院硕士研究生,主要从事新烟碱类杀虫剂环境光化学行为研究.

基金项目：国家”863”项目(2011AA10A207,2013AA065202);国家自然科学基金(21272071);公益性行业(农业)科研专项经费(201103007)

收稿日期：2015-09-12

中图分类号：X703

文献标识码：A

文章编号：1000-6923(2016)04-1112-07